Nonsmearing detergent bar



United States Patent 2,988,511 NONSMEARING DETERGENT BAR Victor Mills,Wyoming, Ohio (The Procter & Gamble Company, R0. Box 175, Cincinnati 31,Ohio), and Edwin 0. Korpi, The Procter 8; Gamble Company, MA & R Bldg,Cincinnati 17, Ohio No Drawing. Filed July 29, 1957, Ser. No. 674,558 8Claims. (Cl. 252-121) This application is a continuation-in-part ofapplication Serial Number 498,433, filed March 31, 1955, and nowabandoned.

The present invention relates to detergent compositions.

More particularly, this invention relates to syntheticdetergent-containing detergent compositions in bar form, characterizedby a unique combination of superior qualities.

A synthetic detergent, to be usable in a bar, must normally be solid atroom temperature. Consequently, the anionic sulfuric reaction productswhich have this characteristic have been considered to possess thegreatest utility for detergent bar applications. However, most of theanionic sulfuric reaction products are also characterized by theundesirable tendency to absorb water from a soap dish, and becomesmeary. This condition can be remedied by combining the syntheticdetergent with a soluble soap and an inert binder material such asstarch, freshly precipitated calcium or magnesium soap, or a waxymaterial, for example, the superglycerinated hard fat described in U.S.Letters Patent 2,175,285, issued to R. A. Duncan and assigned to thepresent applicants assignee. British Patent 689,569 describes the use ofa solid polyethylene glycol of molecular weight 1500-4000, and highmolecular ester (both monoand di-esters) of polyhydric alcohols as abinder substance with synthetic detergents. Many other binder materialsequivalent in physical behavior to any one or more of the foregoing mayalso be used. For example, US. Letters Patent 2,356,903, issued toRichard C. Wood, discloses a binder material comprising parafiin withsuperglycerinated hard fat. In general, any normally solid waxy materialwhich will become plastic under the conditions encountered in themilling of soap may be used.

The use of soluble soap, which has been found to be a very desirableingredient in a bar containing an anionic synthetic detergent, presentsa further problem. In hard water, Whenever the foaming and dispensingpower of the soap has been destroyed by dilution of the soap, thesoluble soap will interact with the calcium and magnesium salts presentin the water to form an insoluble soap curd. Accordingly, the syntheticdetergent should desirably have good curd dispersing characteristics. Inaddition, any bar product must lather well in hard as Well as softwater, it should not crack unduly when, as in normal use, it isalternately wetted and allowed to dry out, and it should be mild to theskin.

A primary object of the present invention is to provide a syntheticdetergent composition in a toilet bar form which will be mild to theskin.

Another object is to provide a synthetic detergent composition whichwill have good curd dispersing characteristics.

It is also an object to provide a detergent bar which will lather wellin hard as well as soft Water.

A further object is to provide a detergent bar which will not crackunduly when, as in normal use, it is alternately wetted and allowed todry out.

The foregoing and other objects can be accomplished by providing adetergent bar containing, as the major anionic organic sulfuric reactionproduct constituent, alkyl glyceryl ether sulfonate, as more fullydefined hereinafter, in combination with soluble soap and a bindermaterial.

The sodium and potassium alkyl glyceryl ether sulfonates are outstandingin their ability to disperse soap curd and in their mildness toward theskin of the user. The sodium and potassium alkyl glyceryl ethersulfonates are somewhat crystalline materials at room temperature, hencethey do not swell and slime unduly when in contact with water. They do,however, dissolve readily in water and form a copious lather. Thiscombination of properties permits the formulation of a toilet bar havingall of the desirable characteristics set forth above.

Alkyl glyceryl ether sulfonates are disclosed in US. Letters Patent2,094,489, granted to Richard Hueter, September 28, 1937. Hueterdescribes the production of these compounds by reacting epichlorohydrinwith an excess of fatty alcohols in the presence of an acid catalyst.The catalyst is removed by Water washing and the product is purified byfractional distillation. The resulting alkyl chloroglyceryl ether isthen reacted with sodium sulfite (the Streckerization reaction) to formthe sodium salt of alkyl glyceryl ether sulfonic acid and sodiumchloride.

The alkyl glyceryl ether sulfonate constituent of the detergentcompositions of this invention are prepared in a manner different fromthat disclosed in the Hueter patent.

It has been found that these alkyl glyceryl ether sulfonates, which arecharacterized by good detersive properties, may be prepared by reactinghigh molecular weight fatty alcohols with an amount of epichlorohydrinwhich is in excess of that required to react with the alcohol to producethe chloromonoglyceryl ether and then sulfonating the resultingchloroglyceryl ethers by means of the Streckerization reaction.

The use of an excess of epichlorohydrin results in the production ofchloroglyceryl ethers in which the glyceryl radical is replaced in partwith polyglyceryl radicals e.g.

with 2 or 3 condensed glyceryl radicals. The formulation of suchpolyglyceryl ethers may be said to progress step-wise in accordance withthe following equations:

The higher polymers, such as the tetrachloro tetraglyceryl ethers mayalso be formed, the amount depending upon the excess of epichlorohydrinwhich is used.

I 3 In any event, the reaction product will comprise a mixture ofmonomer and various proportions of the polymers.

The mixture of chloroglyceryl ethers which is formed in the process canbe represented by the following general formula,

wherein R is an alkyl radical containing from about 10 to about 20carbon atoms and n is an integer from 1 to 4, said mixture comprising atleast 10% of such ethers wherein n is 2. For convenience, thechloroglyceryl ethers wherein n is 1, 2, 3 or 4 will hereinafter bereferred to respectively as the monomer, dimer, dimer and tetramer.

In preparing the alkyl glyceryl ether sulfonate of the invention, theforegoing procedure, utilizing an excess of epichlorohydrin, wasemployed. For example, a fatty alcohol having from about 10 to about 20carbon atoms was reacted with at least a 5% molar excess ofepichlorohydrin in the presence of stannic chloride as a catalyst. Thereaction product was washed free of catalyst and was then reacted withsodium or potassium sulfite (Streckerization).

When the alkyl glyceryl ether sulfonates of the invention are preparedusing the middle cut coconut alcohol, to be discussed hereinafter, it ispreferred that the amount of excess epichlorohydrin be adjusted so as toproduce a chloroglyceryl ether product, which, upon sulfonation, will becharacterized by a dimer content in the range from about to about 30%.Adjustment of the excess epichlorohydrin to produce a product having adimer content within the aforementioned limits will insure the presence,in the chloroglyceryl ether intermediate, of a minimum of unreactedalcohol and of trirner and tetramer fractions.

The presence of large amounts of trimer and tetramer sulfonates in thealkyl glyceryl ether sulfonates prepared from middle cut coconutalcohols is to be avoided because of the reduced detersive activity ofsuch trimerand tetramer-containing compounds in detergent compositions.

It has been found that the amount of dimer specified above, aftersubsequent sulfonation, is sufficient to impart to the products of thisinvention the advantages associated with the presence of the dimer. Inaddition, it has been found that the amount of unreacted alcohol aftersubsequent sulfonation does not significantly modify the advantageousproperties of the alkyl glyceryl ether sulfonates.

During the Streckerization reaction referred to above, sodium orpotassium chloride is formed depending upon whether sodium or potassiumsulfite is used as the Streckerization agent. Normally, the sodium orpotassium chloride is left in the product. Any excess sodium orpotassium sulfite which may be present in the product as a result of theStreckerization reaction is partially converted to the sulfate byoxidation. All of these salts will be referred to hereinaftergenerically as secondary Streckerization produc If desired, salts otherthan the sodium or potassium salts of the alkyl glyceryl ether sulfonicacid can be present in the composition, but the amount present shouldnot have adverse effect on the desired normally solid character of theultimate composition. Such other salts include the calcium, magnesium,ammonium or alkylol substituted ammonium salts which can be preparedfrom the sodium salts for example, by passing a solution of same over anion exchange resin to replace the sodium ion with a hydrogen ion, theresulting acid being neutralized 4 l with calcium or magnesiumhydroxide, ammonia or alkylol-substituted ammonia (alkylol amines).

For the purposes of this invention, saturated fatty alcohols having fromabout 10 to 20 carbon atoms in the alkyl chain, or mixtures thereof,derived from naturally occurring fats and oils, which may include minoramounts of unsaturated alcohols, as well as the 0x0 alcohols, can bereadily used in the preparation of the alkyl glyceryl chloro etherproducts. The middle cut of fatty alcohol mixtures derived from oils ofthe coconut oil group, i.e., the fraction consisting almost entirely ofC and C fatty alcohols, has been found particularly suitable. Forexample, middle cut coconut alcohol is definitive of the alcohol derivedfrom fractionally distilling the alcohols made by the reduction ofcoconut oil, the separated middle fraction having the followingapproximate composition:

Percent C 1 2 C 66 C 23 C16 9 The subscript denotes the number of carbonatoms in the alkyl chain.

The advantages of alkyl glycerol ether sulfonates in the detergent barof this invention begins to be apparent at about 25% of the total of thebars anionic synthetic detergent content. However, it is preferred thatthe alkyl glyceryl ether content be from about 50% to by weight of theorganic anionic sulfuric reaction product and that at least 50% of thealkyl radicals contain about 12 carbon atoms.

Many anionic organic sulfuric reaction products may be advantageouslyused in conjunction with the alkyl glyceryl ether sulfonates. However,these ancillary anionic detergent agents should be selected with somediscretion since they must be adequately water soluble, normally solidat room temperature and should not hydrolyze unduly under conditionswherein they are alternately wetted and dried. The anionic organicsulfuric reaction products which are preferred are the sodium andpotassium salts. Ammonium and substituted ammonium salts tend to producepasty, less-solid materials and should therefore be used only in minorproportions. In addition, it is advisable that the alkyl groups of theactive detergent ingredients be substantially saturated since it hasbeen found that unsaturation in these groups will tend to promote asofter product.

Typical of the large group of water soluble anionic sulfuric organicreaction products which can satsfactorily be used along with alkylglyceryl ether sulfonate are:

The alkyl sulfates, typified by sodium dodecyl sulfate.

The monoglyceride sulfates, such as coconut oil monoglyceride sodiumsulfate. (These are preferably not used with alkaline builders.)

The alkyl ether glycol sulfates, such as coconut alcohol ether ethyleneglycol sodium sulfate.

The alkyl ether monoglyceryl sulfate such as coconut alcoholmonoglycerol sodium sulfate.

The isethionatesfor example, RCOOC H SO Na, where the RC0 radical isderived from an oil of the coconut oil group.

By coconut oil group as used herein is meant the group of tropical nutoils characterized by a predominant content of combined fatty acidshaving 10-14 carbon atoms.

The taurines, for example, RONHC H SO Na, where the RC0 radical isderived from an oil of the coconut oil group.

The sulfo acetates ROOCCH SO Na, where R is an alkyl radical of analcohol derived from an oil of the coconut oil group.

Detergents made by sulfating and neutralizing the compounds made byreacting a fatty amine with hydroxy acetic acid.

The alkyl benzene sulfonates where the alkyl radical has a chain lengthof about 9 to about 15 carbon atoms can also be employed provided theirtendency to exhibit a sticky feel is not objectionable. Mixtures of suchsulfonates with alkyl sulfates wherein at least 50% of the alkylradicals have a chain length of 12 carbon atoms can also be employed.

The water soluble soaps preferably used in the present invention are thesodium salts of fatty acids having a chain length of from about to about18 carbon atoms.

In order to determine the performance characteristics of variousdetergent bar formulations, the following tests, which have beenstandardized for such evaluations, were used. Grading was estimated onan arbitrary scale of 1 to 10, in which 1 is the poorest grade and 10 isthe best grade. It should be noted that this scale has an oppositeconnotations for the overnight smear test only, wherein 1 is consideredthe best grade and 10 is considered the poorest grade.

Inthe tests described below, reference to a water of a certain grainhardness, means the grains per US. gallon expressed as calcium carbonateequivalent.

(1) Bathtub ring and curd test.--1 gram of the detergent compositionbeing tested is dispersed in 100 ml. of 21 grain water at 100 F. in aWaring type blender. This dispersion is then transferred to a 5 literglass funnellike device and 1500 ml. of 21 grain water at 100 F. are runinto the funnel under standard conditions of rate and location of inlet.After 1 minute, the funnel-like device is drained to a volume of 100 ml.in 50 seconds. The amount of curd remaining on the walls of the funneland in the last 100 ml. of the bath is estimated and given a gradeaccording to the beforementioned arbitrary 1-10 scale.

(2) Hand lather technique-1 to 3 drops of standard soil (1 partlanolin-2 parts light mineral oil) is applied to the hands. The handsare lathered under running tap Water (80100 F. controlled within :1 F.)with the test bar. The speed, amount, and character of lather arevisually estimated.

(3) Overnight smear test.-A A" slice is cut from the face of the bar tobe tested by wire cutting or planing. The bar is then weighed. The cutface is placed on two A rods in a dish to which water at 70 F. has beenadded. The dish and bar are kept at 70 F. for 16 hours. The bar is thenremoved and all softened material is wiped from the bar by holding theforefinger as tightly as possible against the softened surface of thebar and moving the finger across the face of the bar with a swipingmotion. The bar is then reweighed and the difference in weight in gramsis reported as grams of smear. It should be noted that contrary to therating of the other characteristics of the bar, where 10 is perfect and1 is very poor, the smear values increase as the bar be,- comes poorer.Hence, the lower the smear value the more desirable the smearcharacteristics of the bar being tested.

I (4) Wet cracks test.-A A" slice is removed from the bar. The cutsurface is then washed until smooth. The washed bar is placed out sideup in water at 70 P. such that the bar surface is submerged in thewater. The bar is allowed to soak for 30 minutes and is then removedfrom the water and dried at 70 F. for 16 hours, with a baflle 1 abovethecut surface and parallel to it. The surface is coated with a carbonblack slurry which is then washed off leaving the black in any cracks.The bar is graded by comparison with a graded series of ten photos ofthe hereinafter defined standard bar.

The relationship of the synthetic detergent, of binder, and of solublesoap in the compositions of the following examples illustrates generallythe useful and practical limits in the practice of the instantinvention. The preferred products of the present invention are thosehaving the following composition limits and which have been processedinto a toilet bar form by the operations normal to the production ofmilled soap in the industry.

15 to 55% anionic sulfuric reaction product of which at least 50% isalkyl glyceryl ether sulfonate 20 to 70% binder 5 to 50% soluble soapThese figures are based on an assumed total of 100%, and the actualtotal percentage of synthetic detergent, of binder, and of soluble soapin the bar will normally be not less than about 75% by Weight of thebar. The remainder of the bar will comprise moisture, perfume, secondaryStreckerization products with or without other ingredients normallyidentified with a detergent toilet bar.

In the examples, in which all parts are by weight, the followingdefinitions apply.

Neat s0ap.The final phase obtained in the kettle boiling method forpreparing soap containing approximately 30% water.

Amalgamator.-A dry-material type mixer which distributes coloringmatter, perfume and other materials, which it may be desired to add,uniformly throughout partially dried soap in the flake or chip form.

Crutcher.A vessel equipped with a strong agitator used for mixing neatsoap with other materials.

In order to judge the performance characteristics of the bars of theexamples, the various numerical grading values set forth can be comparedwith those values appearing below which represent the values obtainedwith a standard soap bar marketed by The Procter & Gamble Company underthe trademark Camay.

Example 1 Parts shown are by weight.

A paste of 12 parts water and 8 parts of sodium alkyl glyceryl ethersulfonate containing about 20% of diglyceryl et-her sulfonates, thealkyl radical being derived from middle cut coconut alcohols, arecombined in a crutcher with a paste of 30 parts Water and 20 parts ofpotassium alkyl sulfate derived from middle cut coconut alcohols. To theresultant mixture is added 25 /2 parts of neat soda soap obtained from amixture of tallow and 20% coconut oil (i.e. about 18 parts real soap and7 parts water). After these materials are well mixed, there is addedslowly with agitation 7.61 parts of Epsom salts (MgSO -7H O), wherebythe sodium soap is converted to the magnesium soap which precipitates inhydrated form. The hydrated magnesium soap possesses superiorcharacteristics as a binder material. The resultant mix is roll driedand the dried product is mixed in an amalgamator With 41 parts of sodiumsoap derived from a mixture of 80% tallow and 20% coconut oil. Thislatter soap is added in the form of pellets containing about 15%moisture. 2.7 parts of sodium chloride is also added to the mix torepress the solution of the alkyl sulfate. The amalgamated mix is thenmilled, extruded and stamped in conventional soap making equipment.

This bar was an improvement over a soap-synthetic bar in which all ofthe active anionic synthetic was alkyl sulfate, and wherein at least 50%of the alkyl groups contained 12 carbon atoms. With alkyl sulfate as thesole active synthetic detergent ingredient, it is necessary to haveabout 40% or more of alkyl sulfate in the bar in order for the bar tohave good curd dispersion properties. These high alkyl sulfate bars weredrying to the skin, i.e. they exhibited the tendency to remove thenatural skin oils, especially when repeatedly used at relatively shorttime intervals such as is encountered in wash stand use. By using 8% ofalkyl glyceryl ether sulfonate in such a toilet bar, the alkyl sulfatecontent of the bar can be cut to 20% without loss of curd dispersion.Such a 20% alkyl sulfate-8% alkyl glyceryl ether sulfonate bar is mildto the skin of the user, and is distinctly superior in this respect tobars containing alkyl sulfate or alkyl benzene sulfonate (averagingabout 12 carbon atoms in the alkyl group) as sole active anionicsynthetic detergent ingredient.

In the preferred products of this invention, which are outstandinglymild and are comparable in this respect to toilet soaps, at least 50% ofthe anionic synthetic detergent should be the alkyl glyceryl ethersulfonate, and the alkyl sulfate and alkyl benzene sulfonate shouldconstitute less than 50% of the anionic synthetic detergent components.A consideration of all performance factors, indicates that bars in whichalkyl glyceryl ether sulfonates predominate over the other anionicsynthetic detergent components are outstandingly superior.

In the following examples, the materials, such as alkyl glycerylsulfonate, and soda soap, are to be understood to connote the pureingredient unless otherwise noted, that is, the Water and inorganicsalts will be listed as such.

Example 2 The following constituents are combined as indicated toproduce a superior toilet bar.

Sodium alkyl glyceryl ether sulfonate derived from middle cut coconutalcohols and containing about of diglyceryl ether sulfonates 36 Sodasoap, 50-50 tallow-coconut soaps 32 Superglycerinated hardenedcottonseed oil 1 18 Secondary Streckerization products 14 1 Thisconstituent had an iodine value of 23 and contained a})out g8%monoglycerides, 43% diglycerides, and 19% trig yceri es.

The above components are placed in an amalgamator, water is added in anamount sufficient upon subsequent mixing, milling, plodding and stampingto give a final product with 9% moisture.

Example 3 A toilet bar having the following formulation is prepared asindicated.

Sodium alkyl glyceryl ether sulfonate derived from middle cut coconutalcohols and containing about The alkyl glyceryl ether sulfonate isbrought into the crutcher in the form of a paste containing about 50%water. The 80% tallow, 20% coconut soap is then added as kettle soap.Calcium chloride in an amount equivalent to that required to convert the80% tallow, 20% coconut soap wholly into calcium soap is added. Duringthe subsequent clutching operation calcium soap and sodium chloride areformed. The resultant crutcher mix is then roll dried. The dried mix isthen put in an amalgamator and the coconut soap, as kettle soap, isadded and well mixed with the dried crutcher mix. The amalgamated mix ismilled, extruded, and stamped in conventional equipment. The resultingdetergent bar contained about moisture and exhibited the followingperformance characteristics.

' Example 4 A superior toilet bar having the following formulation wasprepared as indicated. Parts are by weight.

Parts Sodium alkyl glyceryl ether sulfonate derived from middle cutcoconut alcohols and containing about 20% of diglyceryl ether sulfonate10 Sodium alkyl sulfate from middle cut coconut alcohols 10 Sodium soapof coconut oil 35 Magnesium soap of tallow, 20% coconut oil 20 SecondaryStreckerization products and sodium sulfate from magnesium soappreparation l0 Moisture 15 This was prepared by the method used inExample 3, substituting magnesium sulfate (Epsom salts) for the calciumchloride. The resultant bar had the following performancecharacteristics:

Hand lather 9 Bathtub ring and curd dispersion 10 Overnight smear..grams 2.4 Wet cracks 9.5

One part of the alkyl sulfate in this example can be replaced withpolypropylene benzene sodium sulfonate, in which the polypropyleneradical averages 12 carbon atoms, to give a comparable bar.

Example 5 A toilet bar of the following formulation was prepared asindicated.

Parts Sodium alkyl glyceryl ether sulfonate derived from middle cutcoconut alcohols and containing about Made as in Example 3, that is, the80% tallow20% coconut sodium soap was converted to calcium soap by usingcalcium chloride. This bar tested as follows:

Hand lather 9 Bathtub ring and curd dispersion 9.3 Overnight smear"grams..- 4.5

Instead of the freshly precipitated calcium or magnesium soap as thebinder material, starch can be used to replace all or part. of thecalcium or magnesium soaps with comparable results.

Example 6 A toilet bar of the following formulation is prepared asindicated.

Parts Sodium alkyl glyceryl ether sulfonate derived from middle cutcoconut alcohols and containing about Enough hot water is added to acrutcher initially so that the ultimate crutcher mix will contain from60 to 75% water. The alkyl glyceryl ether sulfonate is added to thecrutcher with rapid agitation until there is thorough dispersion of thematerial. The starch is then added and also dispersed with rapidagitation. The crutcher is then operated at normal speed to achieve agood mix. This mix is then dried on a roll heated with 60 lb. steam.

The roll dried mix is added-to an amalgamator, the sodium 80% tallow,20% coconut oil soap is added as pellets and the sodium coconut soap isadded as kettle soap-about 30% water. The amalgamator charge isthoroughly mixed and is then milled, extruded and stamped inconventional milled soap equipment. The

bar tested as follows:

Hand lather 8 Overnight smear 'grams 9.3

Wet cr Example 7 A toilet bar having the following formulation isprepared as indicated.

Parts Sodium alkyl glyceryl ether sulfonate derived from middle cutcoconut alcohols and containing about The sodium alkyl glyceryl ethersulfonate is dissolved in enough water to constitute 60 to 75% of thefinal crutcher mixture. The 80% tallow, 20% coconut soap to be made intocalcium soap is then dissolved in the soap crutcher. Calcium chloride inan amount equivalent to that required to convert this soap to thecalcium soap is added and agitation is continued until dispersion takesplace. The starch is then added and dispersed with agitation, which iscontinued until all the ingredients are well mixed. The crutcher mix isroll dried. The dried crutcher mix is then amalgamated with pellets ofsodium soap of 80% tallow, 20% coconut oil and with sodium coconut oilsoap as kettle soap. The combined components are milled, plodded andstamped. The hand lather grade of the resulting detergent bar was 8-.

Example 8 A toilet bar having the following formulation is prepared asindicated.

Parts Sodium alkyl glyceryl ether sulfonate derived from middle cutcoconut alcohols and containing about 20% of diglyceryl ether sulfonates20 Sodium soap of coconut oil 35 Oxidized starch 25 SecondaryStreckerization products Water 10 Made as in the case of Example 6, thisbar tested as follows:

Hand lather 9 Bathtub ring and curd dispersion 9 Example 9 A toilet barhaving the following formulation is prepared as indicated.

Parts Potassium alkyl glyceryl ether sulfonates derived from middle cutcoconut alcohols and containing about The potassium alkyl glyceryl ethersulfonate is transferred to the crutcher as a paste, containing about 8%Water. The 80% tallow, 20% coconut oil is added as 10 kettle soapcontaining 35 lbs. of real sodium soap of tallow, 20% coconut oil, and17.5 lbs. of Epsom salts dissolved in water is added. After thoroughagitation to secure complete reaction, the mix is roll dried, milled,

extruded and stamped. This bar tested as follows:

Hand lather 8 Bathtub ring and curd dispersion 9 Overnight smear grams10 Example 10 Parts Sodium alkyl glyceryl ether sulfonates derived frommiddle cut coconut alcohols and containing about 20% of diglyceryl ethersulfonates 25.7 Calcium hardened tallow soap 45.3 Sodium coconut soap5.0 Coconut fatty acid monoethanol amide 2.0

Water and secondary Streckerization products and sodium chloride fromcalcium soap preparation 22.0

This bar tested as follows:

Hand lather grade 7- Bathtub ring and curd dispersion 10 Overnight smeargrams 8+ Wet cracks 10 In this example it will be noted that all of theinsoluble soap is made from tallow and all of the soluble soap is madefrom coconut oil. This is a desirable procedure in a composition with ahigh level of insoluble soap. The soluble soap being of the quicklathering coconut type, tends to overcome the lather repressing effectof the large amount of insoluble soap. Moreover, there is a priceadvantage in using the less expensive tallow for the insoluble soap. Thetallow fatty acids are substantially all of 16 and 18 carbons in chainlength and have a titer between 38 and 45.

In the above formulation three parts of the indicated sodium alkylglyceryl ether sulfonates are replaced with sodium alkyl glyceryl ethersulfonates prepared from substantially completely hydrogenated tallowalcohols and containing about 30% dimer. A synthetic-soap toilet barwith outstanding characteristics is obtained.

Having thus described our invention, What We claim is:

1. A milled detergent bar at least 75 by weight of which consistsessentially of (1) from about 15% to about 55% of normally soliddetergent salts of anionic organic sulfuric reaction products which donot hydrolyze unduly under conditions of alternate Wetting and drying,said salts being selected from the group consisting of the sodium andpotassium salts, and said anionic organic sulfuric reaction productscontaining at least 50% alkyl glyceryl ether sulfonates from about 10%to about 30% of which alkyl glyceryl ether sulfonates are alkyldiglyceryl ether sulfonates, the alkyl radicals containing from about 10to about 20 carbon atoms; (2) from about 5% to about 50% of awater-soluble soap of fatty acids having from about 10 to about 18carbon atoms; and (3) from about 20% to about 70% of a binder materialselected from the group consisting of freshly precipitated calcium soapsof fatty acids having from about 10 to about 18 carbon atoms, freshlyprecipitated magnesium soap of fatty acids having from about 10 to about18 carbon atoms, starch, normally solid waxy materials which will becomeplasic under the conditions encountered in the milling of soap andmixtures thereof.

2. The detergent bar of claim 1 wherein the anionic organic sulfuricreaction product is substantially completely alkyl glyceryl ethersulfonate the alkyl radical of which is derived from middle cut coconutalcohols.

3. The detergent bar of claim 1 wherein the anionic organic sulfuricreaction product is a mixture of alkyl glyceryl ether sulfonate, thealkyl radical of which is derived from middle cut coconut alcohols andalkyl sulfate, the said alkyl glyceryl ether sulfonate and alkyl sulfate11 each containing about 50% of alkyl radicals having 12 carbon atoms.

4. The detergent bar of claim 1 wherein the binder is starch.

5. The detergent bar of claim 1 wherein the binder is magnesium soap.

6. The detergent bar of claim 1 wherein the binder is calcium soap.

7. The detergent bar of claim 1 wherein the soluble soap is derived fromthe fatty acids of coconut oil and the binder is an insoluble soapaveraging from about 16 to 18 carbon atoms in the fatty acid chain andhas a titer ranging from 38 to 45.

8. The detergent bar of claim 1 wherein the anionic organic sulfuricreaction product comprises in combination alkyl glyceryl ethersulfonates and an organic su1 12 furic reaction product selected fromthe group consisting of the water-soluble salts of alkyl sulfuric acid,wherein at least 50% of the alkyl radicals contain 12 carbon atoms,water-soluble salts of alkyl benzene sulfonic acid wherein the alkylradical contains from 9 to 15 carbon atoms, and mixtures thereof.

References Cited in the file of this patent UNITED STATES' PATENTS1,906,484 Nuesslein May 2, 1933 2,094,489 Hueter Sept. 28, 19372,174,761 Schuette et a1 Oct. 3, 1939 2,527,077 Preston Oct. 24, 1950FOREIGN PATENTS 443,559 Great Britain Feb. 17, 1936 UNITED STATES PATENTorricE @E 2'? TlFlQA'lE @F @QRECHN Patent No. 2. 988511 June 13 1961Victor Mills et ale It is hereby certified that error appears in theabove numbered patent requiring correction and that the said LettersPatentv should read as "corrected below,

Column l line 48 for "dispensing"! read dispersing column 4 line 25 forglycerol read glyceryl line 67, for "RONHC H SO Na" read RGONHC H SO Na-g column 5, line 17,, for "connotations" read connotation column 10,line 64,, for "plaeic" read plastic Signed and sealed lllhis lfl fl ghday of November 1961.,

(SEA L) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of PatentsUSCOMM-DC-

1. A MILLED DETERGENT BAR AT LEAST 75% BY WEIGHT OF WHICH CONSISTSESSENTIALLY OF (1) FROM ABOUT 15% TO ABOUT 55% OF NORMALLY SOLIDDETERGENT SALTS OF ANIONIC ORGANIC SULFURIC REACTION PRODUCTS WHICH DONOT HYDROLYZE UNDULY UNDER CONDITIONS OF ALTERNATE WETTING AND DRYING,SAID SALTS BEING SELECTED FROM THE GROUP CONSISTING OF THE SODIUM ANDPOTASSIUM SALTS, AND SAID ANIONIC ORGANIC SULFURIC REACTION PRODUCTSCONTAINING AT LEAST 50% ALKYL GLYCERYL ETHER SULFONATES FROM ABOUT 10%TO ABOUT 30% OF WHICH ALKYL GLYCERYL ETHER SULFONATES ARE ALKYLDIGLYCERYL ETHER SULFONATES, THE ALKYL RADICALS CONTAINING FROM ABOUT 10TO ABOUT 20 CARBON ATOMS, (2) FROM ABOUT 5% TO ABOUT 50% OF AWATER-SOLUBLE SOAP OF FATTY ACIDS HAVING FROM ABOUT 10 TO ABOUT 18CARBON ATOMS, AND (3) FROM ABOUT 20% TO ABOUT 70% OF A BINDER MATERIALSELECTED FROM THE GROUP CONSISTING OF FRESHLY PRECIPITATED CALCIUM SOAPSOF FATTY ACIDS HAVING FROM ABOUT 10 TO ABOUT 18 CARBON ATOMS, FRESHLYPRECIPITATED MAGNESIUM SOAP OF FATTY ACIDS HAVING FROM ABOUT 10 TO ABOUT18 CARBON ATOMS, STARCH, NORMALLY SOLID WAXY MATERIALS WHICH WILL BECOMEPLASIC UNDER THE CONDITIONS ENCOUNTERED IN THE MILLING OF SOAP ANDMIXTURES THEREOF.